N,N,N&#39;-Trimethyl-Bis-(Aminoethyl) Ether and its Derivatives as Catalysts for Polyurethanes

ABSTRACT

The present invention provides compounds produced by the reaction of glycidyl ethers and glycidyl esters with ether compounds including N,N,N′-trimethyl-bis-(aminoethyl) ether. N,N,N′-trimethyl-bis-(aminoethyl) ether and its derivatives can be used as polyurethane catalysts.

BACKGROUND OF THE INVENTION

The present invention relates generally toN,N,N′-trimethyl-bis-(aminoethyl) ether and derivatives thereof,compositions employing such compounds, polyurethane gel and foamformulations, and methods of making polyurethane gels and foams.

Polyurethane foams are widely known and used in automotive, housing andother industries. Such foams are produced by reacting a polyisocyanatewith a polyol in the presence of various additives. One such additive isa chlorofluorocarbon (CFC) blowing agent which vaporizes as a result ofthe reaction exotherm causing the polymerizing mass to form a foam. Thediscovery that CFC's deplete ozone in the stratosphere has resulted inmandates diminishing CFC use. Production of water-blown foams, in whichblowing is performed with CO₂ generated by the reaction of water withthe polyisocyanate, has therefore become increasingly important. Certaintertiary amine catalysts have been used in the production ofpolyurethanes and polyurethane foams. Such tertiary amine catalysts canbe used to accelerate both blowing (reaction of water with polyisocyanteto generate CO₂) and gelling (reaction of polyol with isocyanate).

The ability of the tertiary amine catalyst to selectively promote eitherblowing or gelling is an important consideration in selecting a catalystfor the production of particular polyurethane foam. If a catalystpromotes the blowing reaction too selectively, much of the CO₂ willevolve before sufficient reaction of isocyanate with polyol hasoccurred. As a result, the CO₂ will bubble out of the formulation,resulting in a collapse of the polymerization mass yielding foam of poorquality. In contrast, if a catalyst too strongly promotes the gellingreaction, a substantial portion of the CO₂ will evolve after asignificant degree of polymerization has occurred. Again, poor qualityfoams are produced. These foams are generally characterized by highdensity, broken or poorly defined cells, or other undesirable features.Thus, a balance is needed between reaction of the isocyanate and thepolyol (gelling) and the reaction of the isocyanate with water (blowing)in order to produce a polyurethane foam in which the cells aresubstantially uniform and the foam has suitable properties depending onthe anticipated application; for example, rigid foams, semi-rigid foams,and flexible foams.

Tertiary amine catalysts generally are malodorous and offensive and manyhave high volatility due to their low molecular weight. The release oftertiary amines during foam processing may present safety and toxicityproblems, and the release of residual amines from customer products isgenerally undesirable.

Thus, there exists a need for a catalyst composition that is thermallystable during urethane processing and can produce foams substantiallyfree of volatile amines and/or amine odors. Catalysts containingfunctionalities capable of reacting with isocyanate are desirablebecause they can be immobilized in the polyurethane matrix to yieldproducts substantially free of amine emissions. In addition to theisocyanate reactive site, a high molecular weight moiety that impartslow vapor pressure to the amine catalysts is advantageous. Further, itis beneficial for the catalyst composition to promote a balance betweenthe blowing (water-isocyanate) and gelling (polyol-isocyanate) reactionsin order to produce foams of good quality and acceptable physicalproperties. Accordingly, it is to these ends that the present inventionis directed.

BRIEF SUMMARY OF THE INVENTION

The present invention is directed to novel compounds having at least oneether linkage or moiety and methods of making such compounds. Compoundsin accordance with the present invention have the formula (I):

wherein:

n in each occurrence is selected independently from 1, 2, or 3;

R¹ is a hydrogen atom or a substituted or unsubstituted C₁-C₅ alkyl oralkenyl group;

R^(a) is R² or —COR³; and

R² and R³ are selected independently from a substituted or unsubstitutedC₁-C₂₄ alkyl, alkenyl, aryl, or aralkyl group.

When R^(a) is R², the compounds have the formula (II):

wherein R¹, R², and n are as defined above.

When R^(a) is —COR³, resulting in an ester moiety, the compounds havethe formula (III):

wherein R¹, R³, and n are as defined above.

Additionally, the present invention provides compositions comprising atleast one compound having the formula (IV):

wherein:

n in each occurrence is selected independently from 1, 2, or 3; and

R^(b) is:

or

-   -   c) a hydrogen atom;

R¹ is selected independently from a hydrogen atom or a substituted orunsubstituted C₁-C₅ alkyl or alkenyl group; and

R² and R³ are selected independently from a substituted or unsubstitutedC₁-C₂₄ alkyl, alkenyl, aryl, or aralkyl group.

When R^(b) is a hydrogen atom, the compound has the formula (V):

wherein n in each occurrence is selected independently from 1, 2, or 3.

In one aspect, the compositions comprising at least one compound havingthe formula (IV) are catalyst compositions, with the proviso that when nin each occurrence is 2, R^(b) is not a hydrogen atom. These catalystcompositions can be employed to produce polyurethane gels and/or foams.In another aspect, a composition is provided that comprises the contactproduct of at least one active hydrogen-containing compound and at leastone compound having the formula (IV), with the proviso that when n ineach occurrence is 2, R^(b) is not a hydrogen atom. Yet, in anotheraspect, a composition is provided that comprises the contact product ofat least one active hydrogen-containing compound and at least onecompound having the formula (IV), wherein when n in each occurrence isselected independently from 1, 2, or 3, R^(b) can be a hydrogen atom, anether group, or an ester group, as indicated above. In a further aspect,a composition is provided that comprises the contact product of at leastone additive and at least one compound having the formula (IV), with theproviso that when n in each occurrence is 2, R^(b) is not a hydrogenatom. The at least one additive can be selected from at least onecrosslinker, at least one cell stabilizer, at least one flame retardant,at least one chain extender, at least one epoxy resin, at least oneacrylic resin, at least one filler, at least one pigment, or anycombination thereof. In a still further aspect of the present invention,a composition is provided that comprises the contact product of the atleast one additive and at least one compound having the formula (IV),wherein when n in each occurrence is selected independently from 1, 2,or 3, R^(b) can be a hydrogen atom, an ether group, or an ester group,as indicated above.

The present invention also provides a method of making a polyurethanecomprising contacting at least one polyisocyanate with at least oneactive hydrogen-containing compound in the presence of a catalyticallyeffective amount of a catalyst composition under conditions sufficientto produce the polyurethane. In one aspect, the catalyst compositioncomprises at least one compound having the formula (IV), with theproviso that when n in each occurrence is 2, R^(b) is not a hydrogenatom. In another aspect, the catalyst composition comprises at least onecompound having the formula (IV), wherein when n in each occurrence isselected independently from 1, 2, or 3, R^(b) can be a hydrogen atom, anether group, or an ester group, as indicated above. In a further aspect,a polyurethane foam can be produced when the contacting of the at leastone polyisocyanate and the at least one active hydrogen-containingcompound occurs in the presence of at least one blowing agent and acatalytically effective amount of a catalyst composition of the presentinvention under conditions sufficient to produce the polyurethane foam.

For the production of polyurethane foam, the catalyst composition of thepresent invention offers high activity, promotes a balance between thegelling and blowing reactions, and is substantially free of volatileamines and/or amine odors.

DEFINITIONS

The following definitions are provided in order to aid those skilled inthe art in understanding the detailed description of the presentinvention.

-   -   PUR—polyurethane.    -   Isocyanate Index—The actual amount of polyisocyanate used        divided by the theoretically required stoichiometric amount of        polyisocyanate required to react with all the active hydrogen in        the reaction mixture, multiplied by 100. Also known as (Eq        NCO/Eq of active hydrogen)×100.    -   pphp—parts by weight per hundred weight parts polyol.    -   pbw—parts by weight.    -   TMAEE—N,N,N′-trimethyl-bis-(aminoethyl) ether.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 presents a plot of the foam height versus time for Foam J andFoam K; Foam K was produced using a catalyst system comprisingN,N,N′-trimethyl-N′-(2-hydroxypropyl-butylether)-bis-(aminoethyl) ether(inventive catalyst 4).

FIG. 2 presents a plot of the foam height versus time for Foam J andFoam L; Foam L was produced using a catalyst system comprisingN,N,N′-trimethyl-N′-(2-hydroxypropyl-2-ethylhexylether)-bis-(aminoethyl)ether (inventive catalyst 5).

FIG. 3 presents a plot of the foam height versus time for Foam J andFoam M; Foam M was produced using a catalyst system comprisingN,N,N′-trimethyl-N′-(2-hydroxypropyl-dodecylether)-bis-(aminoethyl)ether andN,N,N′-trimethyl-N′-(2-hydroxypropyl-tetradecylether)-bis-(aminoethyl)ether (inventive catalyst 6).

DETAILED DESCRIPTION OF THE INVENTION

The present invention discloses novel compounds having at least oneether linkage or moiety, and methods of making these new compounds. Thecompounds of the present invention have the formula (I):

wherein:

n in each occurrence is selected independently from 1, 2, or 3;

R¹ is a hydrogen atom or a substituted or unsubstituted C₁-C₅ alkyl oralkenyl group;

R^(a) is R² or —COR³; and

R² and R³ are selected independently from a substituted or unsubstitutedC₁-C₂₄ alkyl, alkenyl, aryl, or aralkyl group.

When R^(a) is R², the compounds have the formula (II):

wherein R¹, R², and n are as defined above.

When R^(a) is —COR³, resulting in an ester moiety, the compounds havethe formula (III):

wherein R¹, R³, and n are as defined above.

Additionally, the present invention provides compositions comprising atleast one compound having the formula (IV):

wherein:

n in each occurrence is selected independently from 1, 2, or 3; and

R^(b) is:

or

-   -   c) a hydrogen atom;

R¹ is selected independently from a hydrogen atom or a substituted orunsubstituted C₁-C₅ alkyl or alkenyl group; and

R² and R³ are selected independently from a substituted or unsubstitutedC₁-C₂₄ alkyl, alkenyl, aryl, or aralkyl group.

When R^(b) is a hydrogen atom, the compounds have the formula (V):

wherein n is as defined above.

In one aspect, the compositions comprising at least one compound havingthe formula (IV) are catalyst compositions, with the proviso that when nin each occurrence is 2, R^(b) is not a hydrogen atom. These catalystcompositions can be employed to produce polyurethane gels and/or foams.In another aspect, a composition is provided that comprises the contactproduct of at least one active hydrogen-containing compound and at leastone compound having the formula (IV), with the proviso that when n ineach occurrence is 2, R^(b) is not a hydrogen atom. Yet, in anotheraspect, a composition is provided that comprises the contact product ofat least one active hydrogen-containing compound and at least onecompound having the formula (IV), wherein when n in each occurrence isselected independently from 1, 2, or 3, R^(b) can be a hydrogen atom, anether group, or an ester group, as indicated above. In a further aspect,a composition is provided that comprises the contact product of at leastone additive and at least one compound having the formula (IV), with theproviso that when n in each occurrence is 2, R^(b) is not a hydrogenatom. The at least one additive can be selected from at least onecrosslinker, at least one cell stabilizer, at least one flame retardant,at least one chain extender, at least one epoxy resin, at least oneacrylic resin, at least one filler, at least one pigment, or anycombination thereof. In a still further aspect of the present invention,a composition is provided that comprises the contact product of the atleast one additive and at least one compound having the formula (IV),wherein when n in each occurrence is selected independently from 1, 2,or 3, R^(b) can be a hydrogen atom, an ether group, or an ester group,as indicated above.

The present invention also provides a method of making a polyurethanecomprising contacting at least one polyisocyanate with at least oneactive hydrogen-containing compound in the presence of a catalyticallyeffective amount of a catalyst composition under conditions sufficientto produce the polyurethane. In one aspect, the catalyst compositioncomprises at least one compound having the formula (IV), with theproviso that when n in each occurrence is 2, R^(b) is not a hydrogenatom. In another aspect, the catalyst composition comprises at least onecompound having the formula (IV), wherein when n in each occurrence isselected independently from 1, 2, or 3, R^(b) can be a hydrogen atom, anether group, or an ester group, as indicated above. In a further aspect,a polyurethane foam can be produced when the contacting of the at leastone polyisocyanate and the at least one active hydrogen-containingcompound occurs in the presence of at least one blowing agent and acatalytically effective amount of a catalyst composition of the presentinvention under conditions sufficient to produce the polyurethane foam.

For the production of polyurethane foam, the catalyst compositions ofthe present invention offer high activity, promote a balance between thegelling and blowing reactions, and are substantially free of volatileamines and/or amine odors.

Applicants disclose several types of ranges in the present invention.These include, but are not limited to, a range of temperatures; a rangeof number of atoms; a range of foam density; a range of IsocyanateIndex; and a range of pphp for the compositions of the presentinvention. When Applicants disclose or claim a range of any type,Applicants' intent is to disclose or claim individually each possiblenumber that such a range could reasonably encompass, as well as anysub-ranges and combinations of sub-ranges encompassed therein. Forexample, when the Applicants disclose or claim a chemical moiety havinga certain number of carbon atoms, Applicants' intent is to disclose orclaim individually every possible number that such a range couldencompass, consistent with the disclosure herein. For example, thedisclosure that “R²” can be an alkyl group having up to 24 carbon atoms,or in alternative language a C₁ to C₂₄ alkyl group, as used herein,refers to a “R²” group that can be selected independently from an alkylgroup having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17,18, 19, 20, 21, 22, 23, or 24 carbon atoms, as well as any range betweenthese two numbers (for example, a C₁ to C₁₈ alkyl group), and alsoincluding any combination of ranges between these two numbers (forexample, a C₃ to C₅ and C₇ to C₁₀ alkyl group). Likewise, this appliesto all other carbon ranges disclosed herein, for example, C₁ to C₅ranges for R¹; alkoxy groups having up to 10 carbon atoms; etc.

Similarly, another representative example follows for the parts byweight of a catalyst composition of the present invention per hundredweight parts of the at least one active hydrogen-containing compound ina foam formulation. If the at least one active hydrogen-containingcompound is an at least one polyol, the parts by weight per hundredweight parts polyol is abbreviated as pphp. Hence, by the disclosurethat the catalyst composition is present in an amount from about 0.01 toabout 20 pphp, for example, Applicants intend to recite that the pphpcan be selected from about 0.01, about 0.02, about 0.03, about 0.04,about 0.05, about 0.06, about 0.07, about 0.08, about 0.09, about 0.1,about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about0.8, about 0.9, about 1, about 2, about 3, about 4, about 5, about 6,about 7, about 8, about 9, about 10, about 11, about 12, about 13, about14, about 15, about 16, about 17, about 18, about 19, or about 20.Likewise, all other ranges disclosed herein are to be interpreted in amanner similar to these two examples.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that may be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference or an interpretation of a reference that Applicants may beunaware of at the time of the filing of the application. Further,Applicants reserve the right to proviso out or exclude any individualsubstituents, analogs, compounds, ligands, structures, or groupsthereof, or any members of a claimed group, if for any reason Applicantschoose to claim less than the full measure of the disclosure, forexample, to account for a reference that Applicants are unaware of atthe time of the filing of the application.

Another aspect of the present invention provides a thermally stablecomposition. When used to describe this feature, a compound is definedas thermally stable at a given temperature when it does not decompose orrelease volatile amines and/or related amine odors at the giventemperature. Compositions of the present invention are thermally stableif they comprise compounds having a secondary amine group and/or asecondary hydroxyl group. Not wishing to be bound by theory, it isgenerally believed that the presence of a secondary amine group and/or asecondary hydroxyl group, which can react with isocyanate, canimmobilize the amine moiety during and after the PUR polymerization.

In one aspect of the present invention, the compositions of the presentinvention have thermal stability up to about 80° C., wherein no orsubstantially no volatile amine compounds are emitted. In a furtheraspect, the compositions of the present invention have thermal stabilityup to about 100° C., up to about 120° C., or up to about 150° C.

The term “contact product” is used herein to describe compositionswherein the components are contacted together in any order, in anymanner, and for any length of time. For example, the components can becontacted by blending or mixing. Further, contacting of any componentcan occur in the presence or absence of any other component of thecompositions or foam formulations described herein. Combining additionalcomponents of a composition or a foam formulation can be achieved by anymethod known to one of skill in the art.

While compositions and methods are described in terms of “comprising”various components or steps, the compositions and methods can also“consist essentially of” or “consist of” the various components orsteps.

Compounds Having the Formula (II)

The present invention discloses new compounds having at least one etherlinkage or moiety, as illustrated by the formula (I):

wherein:

n in each occurrence is selected independently from 1, 2, or 3;

R¹ is a hydrogen atom or a substituted or unsubstituted C₁C-₅ alkyl oralkenyl group;

R^(a) is R² or —COR³; and

R² and R³ are selected independently from a substituted or unsubstitutedC₁-C₂₄ alkyl, alkenyl, aryl, or aralkyl group.

In one aspect of the present invention, R^(a) is R² and the newcompounds have the formula (II):

wherein R¹, R², and n are as defined in formula (I) above.

Unless otherwise specified, alkyl and alkenyl groups described hereinare intended to include all structural isomers, linear or branched, of agiven structure; for example, all enantiomers and all diasteriomers areincluded within this definition. As an example, unless otherwisespecified, the term propyl is meant to include n-propyl and iso-propyl,while the term butyl is meant to include n-butyl, iso-butyl, t-butyl,sec-butyl, and so forth. For instance, non-limiting examples of octylisomers include 2-ethylhexyl and neooctyl. Similarly, substituted alkyl,alkenyl, aryl, and aralkyl groups described herein are intended toinclude substituted analogs of a given structure. For example, thesubstituents on alkyl, alkenyl, aryl, and aralkyl groups can include,but are not limited to, halides; hydroxyl groups; amino groups; alkoxy,alkylamino, or dialkylamino groups having up to 10 carbon atoms; orcombinations thereof.

Non-limiting examples of alkyl groups which can be present in newcompounds having the formula (II) include methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, or decyl, and the like. Examples ofalkenyl groups within the scope of the present invention include, butare not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, nonenyl, decenyl, and the like. Aryl and aralkyl(aralkyl is defined as an aryl-substituted alkyl or arylalkyl) groupsinclude phenyl, alkyl-substituted phenyl, naphthyl, alkyl-substitutednaphthyl, and the like. For example, non-limiting examples of aryl andaralkyl groups useful in the present invention include, but are notlimited to, phenyl, tolyl, benzyl, dimethylphenyl, trimethylphenyl,phenylethyl, phenylpropyl, phenylbutyl, propyl-2-phenylethyl, and thelike.

According to various aspects of this invention, this disclosure providescompounds according to formula (II), which include but are not limitedto, compounds wherein n, R¹, and R² can be selected according toFormulas (A-01) through (A-264) in Table I.

TABLE I Exemplary selections for n, R¹, and R² for compounds accordingto this invention, having the formula (II). Formula n R¹ R² A-01 1hydrogen ethyl A-02 2 hydrogen ethyl A-03 3 hydrogen ethyl A-04 1hydrogen n-propyl A-05 2 hydrogen n-propyl A-06 3 hydrogen n-propyl A-071 hydrogen iso-propyl A-08 2 hydrogen iso-propyl A-09 3 hydrogeniso-propyl A-10 1 hydrogen n-butyl A-11 2 hydrogen n-butyl A-12 3hydrogen n-butyl A-13 1 hydrogen iso-butyl A-14 2 hydrogen iso-butylA-15 3 hydrogen iso-butyl A-16 1 hydrogen t-butyl A-17 2 hydrogent-butyl A-18 3 hydrogen t-butyl A-19 1 hydrogen sec-butyl A-20 2hydrogen sec-butyl A-21 3 hydrogen sec-butyl A-22 1 hydrogen pentyl A-232 hydrogen pentyl A-24 3 hydrogen pentyl A-25 1 hydrogen iso-pentyl A-262 hydrogen iso-pentyl A-27 3 hydrogen iso-pentyl A-28 1 hydrogenneopentyl A-29 2 hydrogen neopentyl A-30 3 hydrogen neopentyl A-31 1hydrogen hexyl A-32 2 hydrogen hexyl A-33 3 hydrogen hexyl A-34 1hydrogen neohexyl A-35 2 hydrogen neohexyl A-36 3 hydrogen neohexyl A-371 hydrogen heptyl A-38 2 hydrogen heptyl A-39 3 hydrogen heptyl A-40 1hydrogen neoheptyl A-41 2 hydrogen neoheptyl A-42 3 hydrogen neoheptylA-43 1 hydrogen octyl A-44 2 hydrogen octyl A-45 3 hydrogen octyl A-46 1hydrogen 2-ethylhexyl A-47 2 hydrogen 2-ethylhexyl A-48 3 hydrogen2-ethylhexyl A-49 1 hydrogen neooctyl A-50 2 hydrogen neooctyl A-51 3hydrogen neooctyl A-52 1 hydrogen nonyl A-53 2 hydrogen nonyl A-54 3hydrogen nonyl A-55 1 hydrogen neononyl A-56 2 hydrogen neononyl A-57 3hydrogen neononyl A-58 1 hydrogen decyl A-59 2 hydrogen decyl A-60 3hydrogen decyl A-61 1 hydrogen neodecyl A-62 2 hydrogen neodecyl A-63 3hydrogen neodecyl A-64 1 hydrogen dodecyl A-65 2 hydrogen dodecyl A-66 3hydrogen dodecyl A-67 1 hydrogen neododecyl A-68 2 hydrogen neododecylA-69 3 hydrogen neododecyl A-70 1 hydrogen tetradecyl A-71 2 hydrogentetradecyl A-72 3 hydrogen tetradecyl A-73 1 hydrogen hexadecyl A-74 2hydrogen hexadecyl A-75 3 hydrogen hexadecyl A-76 1 hydrogen octadecylA-77 2 hydrogen octadecyl A-78 3 hydrogen octadecyl A-79 1 hydrogenethenyl A-80 2 hydrogen ethenyl A-81 3 hydrogen ethenyl A-82 1 hydrogenpropenyl A-83 2 hydrogen propenyl A-84 3 hydrogen propenyl A-85 1hydrogen butenyl A-86 2 hydrogen butenyl A-87 3 hydrogen butenyl A-88 1hydrogen pentenyl A-89 2 hydrogen pentenyl A-90 3 hydrogen pentenyl A-911 hydrogen hexenyl A-92 2 hydrogen hexenyl A-93 3 hydrogen hexenyl A-941 hydrogen heptenyl A-95 2 hydrogen heptenyl A-96 3 hydrogen heptenylA-97 1 hydrogen octenyl A-98 2 hydrogen octenyl A-99 3 hydrogen octenylA-100 1 hydrogen nonenyl A-101 2 hydrogen nonenyl A-102 3 hydrogennonenyl A-103 1 hydrogen decenyl A-104 2 hydrogen decenyl A-105 3hydrogen decenyl A-106 1 hydrogen phenyl A-107 2 hydrogen phenyl A-108 3hydrogen phenyl A-109 1 hydrogen tolyl A-110 2 hydrogen tolyl A-111 3hydrogen tolyl A-112 1 hydrogen benzyl A-113 2 hydrogen benzyl A-114 3hydrogen benzyl A-115 1 hydrogen dimethylphenyl A-116 2 hydrogendimethylphenyl A-117 3 hydrogen dimethylphenyl A-118 1 hydrogentrimethylphenyl A-119 2 hydrogen trimethylphenyl A-120 3 hydrogentrimethylphenyl A-121 1 hydrogen phenylethyl A-122 2 hydrogenphenylethyl A-123 3 hydrogen phenylethyl A-124 1 hydrogen phenylpropylA-125 2 hydrogen phenylpropyl A-126 3 hydrogen phenylpropyl A-127 1hydrogen phenylbutyl A-128 2 hydrogen phenylbutyl A-129 3 hydrogenphenylbutyl A-130 1 hydrogen propyl-2-phenylethyl A-131 2 hydrogenpropyl-2-phenylethyl A-132 3 hydrogen propyl-2-phenylethyl A-133 1methyl ethyl A-134 2 methyl ethyl A-135 3 methyl ethyl A-136 1 methyln-propyl A-137 2 methyl n-propyl A-138 3 methyl n-propyl A-139 1 methyliso-propyl A-140 2 methyl iso-propyl A-141 3 methyl iso-propyl A-142 1methyl n-butyl A-143 2 methyl n-butyl A-144 3 methyl n-butyl A-145 1methyl iso-butyl A-146 2 methyl iso-butyl A-147 3 methyl iso-butyl A-1481 methyl t-butyl A-149 2 methyl t-butyl A-150 3 methyl t-butyl A-151 1methyl sec-butyl A-152 2 methyl sec-butyl A-153 3 methyl sec-butyl A-1541 methyl pentyl A-155 2 methyl pentyl A-156 3 methyl pentyl A-157 1methyl iso-pentyl A-158 2 methyl iso-pentyl A-159 3 methyl iso-pentylA-160 1 methyl neopentyl A-161 2 methyl neopentyl A-162 3 methylneopentyl A-163 1 methyl hexyl A-164 2 methyl hexyl A-165 3 methyl hexylA-166 1 methyl neohexyl A-167 2 methyl neohexyl A-168 3 methyl neohexylA-169 1 methyl heptyl A-170 2 methyl heptyl A-171 3 methyl heptyl A-1721 methyl neoheptyl A-173 2 methyl neoheptyl A-174 3 methyl neoheptylA-175 1 methyl octyl A-176 2 methyl octyl A-177 3 methyl octyl A-178 1methyl 2-ethylhexyl A-179 2 methyl 2-ethylhexyl A-180 3 methyl2-ethylhexyl A-181 1 methyl neooctyl A-182 2 methyl neooctyl A-183 3methyl neooctyl A-184 1 methyl nonyl A-185 2 methyl nonyl A-186 3 methylnonyl A-187 1 methyl neononyl A-188 2 methyl neononyl A-189 3 methylneononyl A-190 1 methyl decyl A-191 2 methyl decyl A-192 3 methyl decylA-193 1 methyl neodecyl A-194 2 methyl neodecyl A-195 3 methyl neodecylA-196 1 methyl dodecyl A-197 2 methyl dodecyl A-198 3 methyl dodecylA-199 1 methyl neododecyl A-200 2 methyl neododecyl A-201 3 methylneododecyl A-202 1 methyl tetradecyl A-203 2 methyl tetradecyl A-204 3methyl tetradecyl A-205 1 methyl hexadecyl A-206 2 methyl hexadecylA-207 3 methyl hexadecyl A-208 1 methyl octadecyl A-209 2 methyloctadecyl A-210 3 methyl octadecyl A-211 1 methyl ethenyl A-212 2 methylethenyl A-213 3 methyl ethenyl A-214 1 methyl propenyl A-215 2 methylpropenyl A-216 3 methyl propenyl A-217 1 methyl butenyl A-218 2 methylbutenyl A-219 3 methyl butenyl A-220 1 methyl pentenyl A-221 2 methylpentenyl A-222 3 methyl pentenyl A-223 1 methyl hexenyl A-224 2 methylhexenyl A-225 3 methyl hexenyl A-226 1 methyl heptenyl A-227 2 methylheptenyl A-228 3 methyl heptenyl A-229 1 methyl octenyl A-230 2 methyloctenyl A-231 3 methyl octenyl A-232 1 methyl nonenyl A-233 2 methylnonenyl A-234 3 methyl nonenyl A-235 1 methyl decenyl A-236 2 methyldecenyl A-237 3 methyl decenyl A-238 1 methyl phenyl A-239 2 methylphenyl A-240 3 methyl phenyl A-241 1 methyl tolyl A-242 2 methyl tolylA-243 3 methyl tolyl A-244 1 methyl benzyl A-245 2 methyl benzyl A-246 3methyl benzyl A-247 1 methyl dimethylphenyl A-248 2 methyldimethylphenyl A-249 3 methyl dimethylphenyl A-250 1 methyltrimethylphenyl A-251 2 methyl trimethylphenyl A-252 3 methyltrimethylphenyl A-253 1 methyl phenylethyl A-254 2 methyl phenylethylA-255 3 methyl phenylethyl A-256 1 methyl phenylpropyl A-257 2 methylphenylpropyl A-258 3 methyl phenylpropyl A-259 1 methyl phenylbutylA-260 2 methyl phenylbutyl A-261 3 methyl phenylbutyl A-262 1 methylpropyl-2-phenylethyl A-263 2 methyl propyl-2-phenylethyl A-264 3 methylpropyl-2-phenylethyl Notes: (1) Table I only specifies compounds where nis the same in each occurrence. (2) If an isomeric form of R² is notspecified, that selection of R² is meant to include all isomeric forms,even if some or all specific isomeric forms are additionally specifiedin Table I. For example, the selection of octyl is meant to include allisomeric versions of octyl, even though 2-ethylhexyl and neooctyl arespecifically listed.

In another aspect, R¹ in the compounds having the formula (II) is ahydrogen atom or a methyl group. In yet another aspect, R² is a methyl,an ethyl, a propyl, a butyl, a pentyl, a hexyl, a heptyl, an octyl, a2-ethylhexyl, a nonyl, a decyl, a dodecyl, a tetradecyl, a hexadecyl, anoctadecyl, a phenyl, a tolyl, or a benzyl group. In still anotheraspect, n equals 2 in each occurrence.

Illustrative examples of compounds having the formula (II) include, butare not limited to:N,N,N′-trimethyl-N′-(2-hydroxypropyl-butylether)-bis-(aminoethyl) ether;N,N,N′-trimethyl-N′-(2-hydroxypropyl-hexylether)-bis-(aminoethyl) ether;N,N,N′-trimethyl-N′-(2-hydroxypropyl-2-ethylhexylether)-bis-(aminoethyl)ether;N,N,N′-trimethyl-N′-(2-hydroxypropyl-dodecylether)-bis-(aminoethyl)ether;N,N,N′-trimethyl-N′-(2-hydroxypropyl-tetradecylether)-bis-(aminoethyl)ether;N,N,N′-trimethyl-N′-(2-hydroxypropyl-hexadecylether)-bis-(aminoethyl)ether;N,N,N′-trimethyl-N′-(2-hydroxypropyl-benzylether)-bis-(aminoethyl);N,N-Dimethylaminopropyl-N′-methyl-N′-(2-hydroxypropyl-butylether)aminoethylether;N,N-Dimethylaminopropyl-N′-methyl-N′-(2-hydroxypropyl-2-ethylhexylether)aminoethylether;N,N-Dimethylaminopropyl-N′-methyl-N′-(2-hydroxypropyl-dodecylether)aminoethylether;N,N-Dimethylaminopropyl-N′-methyl-N′-(2-hydroxypropyl-tetradecylether)aminoethylether; and the like.

In accordance with the present invention, a method of making these novelcompounds is disclosed. For example, compounds having the formula (II)can be synthesized in accordance with Reaction Scheme A:

wherein R¹, R², and n are as defined in formulas (II) and (V) above.

First, one reactant in Reaction Scheme A is illustrated in the formula(V),

When n equals 2 in each occurrence, the compound having the formula (V)is N,N,N′-trimethyl-bis-(aminoethyl) ether (abbreviated TMAEE). ReactantTMAEE is placed in a temperature-controlled flask with a stir bar and areflux condenser. TMAEE is heated and a glycidyl ether is added to theflask containing TMAEE and the mixture is stirred substantiallyconstantly. The glycidyl ether can be added to the TMAEE rapidly (i.e.,in a few seconds) or slowly added over a period of several hours. Inanother aspect, the glycidyl ether is added slowly over the course ofabout 30 minutes, about 1 hour, about 90 minutes, or about 2 hours.Prior to the addition of the glycidyl ether, TMAEE is heated to atemperature in the range of about 50° C. to about 250° C. While thisreaction is exothermic, the initial temperature can be maintainedsubstantially constant during the addition of the glycidyl ether. Infurther aspect of the present invention, TMAEE is heated to andcontrolled at a temperature in the range of about 80° C. to about 150°C. during the addition of the glycidyl ether.

Once the addition of the glycidyl ether is complete, the reactionmixture can be controlled at a temperature in the range of about 50° C.to about 250° C. In yet another aspect, the reaction mixture can becontrolled at a temperature in the range of about 80° C. to about 150°C. The time that it takes for this reaction to reach completion isdependent upon the reaction temperature. The reaction mixture can betested by gas chromatography (GC), or other analytical methods, todetermine when the ether compound having the formula (V)—in this case,TMAEE—has been completely consumed. It is within the scope of thepresent invention to use an excess of TMAEE reactant, or an excess ofthe glycidyl ether reactant. However, molar ratios that varysignificantly from a molar ratio of about 1:1 can lead to excess unusedreactants and potentially unwanted side reactions. Non-limiting examplesof the synthesis of new compounds having the formula (II) in accordancewith the present invention are illustrated in Examples 4-6 that follow.

Compounds Having the Formula (III)

Novel compounds having the formula (I) are disclosed in the presentinvention:

wherein:

n in each occurrence is selected independently from 1, 2, or 3;

R¹ is a hydrogen atom or a substituted or unsubstituted C₁-C₅ alkyl oralkenyl group;

R^(a) is R² or —COR³; and

R² and R³ are selected independently from a substituted or unsubstitutedC₁-C₂₄ alkyl, alkenyl, aryl, or aralkyl group.

In another aspect of the present invention, R^(a) is —COR³ resulting inan ester moiety and novel compounds having the formula (III):

wherein R¹, R³, and n are as defined in formula (I) immediately above.

Unless otherwise specified, alkyl and alkenyl groups described hereinare intended to include all structural isomers, linear or branched, of agiven structure; for example, all enantiomers and all diasteriomers areincluded within this definition. As an example, unless otherwisespecified, the term propyl is meant to include n-propyl and iso-propyl,while the term butyl is meant to include n-butyl, iso-butyl, t-butyl,sec-butyl, and so forth. For instance, non-limiting examples of octylisomers include 2-ethylhexyl and neooctyl. Similarly, substituted alkyl,alkenyl, aryl, and aralkyl groups described herein are intended toinclude substituted analogs of a given structure. For example, thesubstituents on alkyl, alkenyl, aryl, and aralkyl groups can include,but are not limited to, halides; hydroxyl groups; amino groups; alkoxy,alkylamino, or dialkylamino groups having up to 10 carbon atoms; orcombinations thereof.

Non-limiting examples of alkyl groups which can be present in compoundshaving the formula (III) include methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, or decyl, and the like. Examples of alkenylgroups within the scope of the present invention include, but are notlimited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl,octenyl, nonenyl, decenyl, and the like. Aryl and aralkyl (aralkyl isdefined as an aryl-substituted alkyl or arylalkyl) groups includephenyl, alkyl-substituted phenyl, naphthyl, alkyl-substituted naphthyl,and the like. For example, non-limiting examples of aryl and aralkylgroups useful in the present invention include, but are not limited to,phenyl, tolyl, benzyl, dimethylphenyl, trimethylphenyl, phenylethyl,phenylpropyl, phenylbutyl, propyl-2-phenylethyl, and the like.

According to various aspects of this invention, this disclosure providescompounds according to formula (III), which include, but are not limitedto, compounds wherein n, R¹, and R³ can be selected according toFormulas (B-01) through (B-264) in Table II.

TABLE II Exemplary selections for n, R¹, and R³ for compounds accordingto this invention, having the formula (III). Formula n R¹ R³ B-01 1hydrogen ethyl B-02 2 hydrogen ethyl B-03 3 hydrogen ethyl B-04 1hydrogen n-propyl B-05 2 hydrogen n-propyl B-06 3 hydrogen n-propyl B-071 hydrogen iso-propyl B-08 2 hydrogen iso-propyl B-09 3 hydrogeniso-propyl B-10 1 hydrogen n-butyl B-11 2 hydrogen n-butyl B-12 3hydrogen n-butyl B-13 1 hydrogen iso-butyl B-14 2 hydrogen iso-butylB-15 3 hydrogen iso-butyl B-16 1 hydrogen t-butyl B-17 2 hydrogent-butyl B-18 3 hydrogen t-butyl B-19 1 hydrogen sec-butyl B-20 2hydrogen sec-butyl B-21 3 hydrogen sec-butyl B-22 1 hydrogen pentyl B-232 hydrogen pentyl B-24 3 hydrogen pentyl B-25 1 hydrogen iso-pentyl B-262 hydrogen iso-pentyl B-27 3 hydrogen iso-pentyl B-28 1 hydrogenneopentyl B-29 2 hydrogen neopentyl B-30 3 hydrogen neopentyl B-31 1hydrogen hexyl B-32 2 hydrogen hexyl B-33 3 hydrogen hexyl B-34 1hydrogen neohexyl B-35 2 hydrogen neohexyl B-36 3 hydrogen neohexyl B-371 hydrogen heptyl B-38 2 hydrogen heptyl B-39 3 hydrogen heptyl B-40 1hydrogen neoheptyl B-41 2 hydrogen neoheptyl B-42 3 hydrogen neoheptylB-43 1 hydrogen octyl B-44 2 hydrogen octyl B-45 3 hydrogen octyl B-46 1hydrogen 2-ethylhexyl B-47 2 hydrogen 2-ethylhexyl B-48 3 hydrogen2-ethylhexyl B-49 1 hydrogen neooctyl B-50 2 hydrogen neooctyl B-51 3hydrogen neooctyl B-52 1 hydrogen nonyl B-53 2 hydrogen nonyl B-54 3hydrogen nonyl B-55 1 hydrogen neononyl B-56 2 hydrogen neononyl B-57 3hydrogen neononyl B-58 1 hydrogen decyl B-59 2 hydrogen decyl B-60 3hydrogen decyl B-61 1 hydrogen neodecyl B-62 2 hydrogen neodecyl B-63 3hydrogen neodecyl B-64 1 hydrogen dodecyl B-65 2 hydrogen dodecyl B-66 3hydrogen dodecyl B-67 1 hydrogen neododecyl B-68 2 hydrogen neododecylB-69 3 hydrogen neododecyl B-70 1 hydrogen tetradecyl B-71 2 hydrogentetradecyl B-72 3 hydrogen tetradecyl B-73 1 hydrogen hexadecyl B-74 2hydrogen hexadecyl B-75 3 hydrogen hexadecyl B-76 1 hydrogen octadecylB-77 2 hydrogen octadecyl B-78 3 hydrogen octadecyl B-79 1 hydrogenethenyl B-80 2 hydrogen ethenyl B-81 3 hydrogen ethenyl B-82 1 hydrogenpropenyl B-83 2 hydrogen propenyl B-84 3 hydrogen propenyl B-85 1hydrogen butenyl B-86 2 hydrogen butenyl B-87 3 hydrogen butenyl B-88 1hydrogen pentenyl B-89 2 hydrogen pentenyl B-90 3 hydrogen pentenyl B-911 hydrogen hexenyl B-92 2 hydrogen hexenyl B-93 3 hydrogen hexenyl B-941 hydrogen heptenyl B-95 2 hydrogen heptenyl B-96 3 hydrogen heptenylB-97 1 hydrogen octenyl B-98 2 hydrogen octenyl B-99 3 hydrogen octenylB-100 1 hydrogen nonenyl B-101 2 hydrogen nonenyl B-102 3 hydrogennonenyl B-103 1 hydrogen decenyl B-104 2 hydrogen decenyl B-105 3hydrogen decenyl B-106 1 hydrogen phenyl B-107 2 hydrogen phenyl B-108 3hydrogen phenyl B-109 1 hydrogen tolyl B-110 2 hydrogen tolyl B-111 3hydrogen tolyl B-112 1 hydrogen benzyl B-113 2 hydrogen benzyl B-114 3hydrogen benzyl B-115 1 hydrogen dimethylphenyl B-116 2 hydrogendimethylphenyl B-117 3 hydrogen dimethylphenyl B-118 1 hydrogentrimethylphenyl B-119 2 hydrogen trimethylphenyl B-120 3 hydrogentrimethylphenyl B-121 1 hydrogen phenylethyl B-122 2 hydrogenphenylethyl B-123 3 hydrogen phenylethyl B-124 1 hydrogen phenylpropylB-125 2 hydrogen phenylpropyl B-126 3 hydrogen phenylpropyl B-127 1hydrogen phenylbutyl B-128 2 hydrogen phenylbutyl B-129 3 hydrogenphenylbutyl B-130 1 hydrogen propyl-2-phenylethyl B-131 2 hydrogenpropyl-2-phenylethyl B-132 3 hydrogen propyl-2-phenylethyl B-133 1methyl ethyl B-134 2 methyl ethyl B-135 3 methyl ethyl B-136 1 methyln-propyl B-137 2 methyl n-propyl B-138 3 methyl n-propyl B-139 1 methyliso-propyl B-140 2 methyl iso-propyl B-141 3 methyl iso-propyl B-142 1methyl n-butyl B-143 2 methyl n-butyl B-144 3 methyl n-butyl B-145 1methyl iso-butyl B-146 2 methyl iso-butyl B-147 3 methyl iso-butyl B-1481 methyl t-butyl B-149 2 methyl t-butyl B-150 3 methyl t-butyl B-151 1methyl sec-butyl B-152 2 methyl sec-butyl B-153 3 methyl sec-butyl B-1541 methyl pentyl B-155 2 methyl pentyl B-156 3 methyl pentyl B-157 1methyl iso-pentyl B-158 2 methyl iso-pentyl B-159 3 methyl iso-pentylB-160 1 methyl neopentyl B-161 2 methyl neopentyl B-162 3 methylneopentyl B-163 1 methyl hexyl B-164 2 methyl hexyl B-165 3 methyl hexylB-166 1 methyl neohexyl B-167 2 methyl neohexyl B-168 3 methyl neohexylB-169 1 methyl heptyl B-170 2 methyl heptyl B-171 3 methyl heptyl B-1721 methyl neoheptyl B-173 2 methyl neoheptyl B-174 3 methyl neoheptylB-175 1 methyl octyl B-176 2 methyl octyl B-177 3 methyl octyl B-178 1methyl 2-ethylhexyl B-179 2 methyl 2-ethylhexyl B-180 3 methyl2-ethylhexyl B-181 1 methyl neooctyl B-182 2 methyl neooctyl B-183 3methyl neooctyl B-184 1 methyl nonyl B-185 2 methyl nonyl B-186 3 methylnonyl B-187 1 methyl neononyl B-188 2 methyl neononyl B-189 3 methylneononyl B-190 1 methyl decyl B-191 2 methyl decyl B-192 3 methyl decylB-193 1 methyl neodecyl B-194 2 methyl neodecyl B-195 3 methyl neodecylB-196 1 methyl dodecyl B-197 2 methyl dodecyl B-198 3 methyl dodecylB-199 1 methyl neododecyl B-200 2 methyl neododecyl B-201 3 methylneododecyl B-202 1 methyl tetradecyl B-203 2 methyl tetradecyl B-204 3methyl tetradecyl B-205 1 methyl hexadecyl B-206 2 methyl hexadecylB-207 3 methyl hexadecyl B-208 1 methyl octadecyl B-209 2 methyloctadecyl B-210 3 methyl octadecyl B-211 1 methyl ethenyl B-212 2 methylethenyl B-213 3 methyl ethenyl B-214 1 methyl propenyl B-215 2 methylpropenyl B-216 3 methyl propenyl B-217 1 methyl butenyl B-218 2 methylbutenyl B-219 3 methyl butenyl B-220 1 methyl pentenyl B-221 2 methylpentenyl B-222 3 methyl pentenyl B-223 1 methyl hexenyl B-224 2 methylhexenyl B-225 3 methyl hexenyl B-226 1 methyl heptenyl B-227 2 methylheptenyl B-228 3 methyl heptenyl B-229 1 methyl octenyl B-230 2 methyloctenyl B-231 3 methyl octenyl B-232 1 methyl nonenyl B-233 2 methylnonenyl B-234 3 methyl nonenyl B-235 1 methyl decenyl B-236 2 methyldecenyl B-237 3 methyl decenyl B-238 1 methyl phenyl B-239 2 methylphenyl B-240 3 methyl phenyl B-241 1 methyl tolyl B-242 2 methyl tolylB-243 3 methyl tolyl B-244 1 methyl benzyl B-245 2 methyl benzyl B-246 3methyl benzyl B-247 1 methyl dimethylphenyl B-248 2 methyldimethylphenyl B-249 3 methyl dimethylphenyl B-250 1 methyltrimethylphenyl B-251 2 methyl trimethylphenyl B-252 3 methyltrimethylphenyl B-253 1 methyl phenylethyl B-254 2 methyl phenylethylB-255 3 methyl phenylethyl B-256 1 methyl phenylpropyl B-257 2 methylphenylpropyl B-258 3 methyl phenylpropyl B-259 1 methyl phenylbutylB-260 2 methyl phenylbutyl B-261 3 methyl phenylbutyl B-262 1 methylpropyl-2-phenylethyl B-263 2 methyl propyl-2-phenylethyl B-264 3 methylpropyl-2-phenylethyl Notes: (1) Table II only specifies compounds wheren is the same in each occurrence. (2) If an isomeric form of R³ is notspecified, that selection of R³ is meant to include all isomeric forms,even if some or all specific isomeric forms are additionally specifiedin Table II. For example, the selection of octyl is meant to include allisomeric versions of octyl, even though 2-ethylhexyl and neooctyl arespecifically listed.

In another aspect, R¹ in the compounds having the formula (III) is ahydrogen atom or a methyl group. In yet another aspect, R³ is a methyl,an ethyl, a propyl, a butyl, a pentyl, a hexyl, a heptyl, an octyl, a2-ethylhexyl, a nonyl, a decyl, a dodecyl, a tetradecyl, a hexadecyl, anoctadecyl, a phenyl, a tolyl, or a benzyl group. In still anotheraspect, the integer n equals 2 in each occurrence.

Illustrative examples of the new compounds having the formula (III)include, but are not limited to:N,N,N′-trimethyl-N′-(2-hydroxypropyl-butylester)-bis-(aminoethyl) ether;N,N,N′-trimethyl-N′-(2-hydroxypropyl-2-ethylhexylester)-bis-(aminoethyl)ether;N,N,N′-trimethyl-N′-(2-hydroxypropyl-neodecylester)-bis-(aminoethyl)ether;N,N,N′-trimethyl-N′-(2-hydroxypropyl-dodecylester)-bis-(aminoethyl)ether;N,N,N′-trimethyl-N′-(2-hydroxypropyl-tetradecylester)-bis-(aminoethyl)ether;N,N,N′-trimethyl-N′-(2-hydroxypropyl-octadecylester)-bis-(aminoethyl)ether;N,N,N′-trimethyl-N′-(2-hydroxypropyl-benzylester)-bis-(aminoethyl)ether;N,N-Dimethylaminopropyl-N′-methyl-N′-(2-hydroxypropyl-butylester)aminoethylether;N,N-Dimethylaminopropyl-N′-methyl-N′-(2-hydroxypropyl-2-ethylhexylester)aminoethylether;N,N-Dimethylaminopropyl-N′-methyl-N′-(2-hydroxypropyl-dodecylester)aminoethylether;N,N-Dimethylaminopropyl-N′-methyl-N′-(2-hydroxypropyl-tetradecylester)aminoethylether; and the like.

In accordance with the present invention, a method of making these novelcompounds is disclosed. For example, compounds having the formula (III)can be synthesized in accordance with Reaction Scheme B:

wherein R¹, R³, and n are as defined in formulas (III) and (V) above.

First, one reactant in Reaction Scheme B is illustrated in the formula(V),

When n equals 2 in each occurrence, the compound having the formula (V)is TMAEE. Reactant TMAEE is placed in a temperature-controlled flaskwith a stir bar and a reflux condenser. TMAEE is heated and a glycidylester is added to the flask containing TMAEE and the mixture is stirredsubstantially constantly. The glycidyl ester can be added to the TMAEErapidly (i.e., in a few seconds) or slowly added over the period ofseveral hours. In another aspect, the glycidyl ester is added slowlyover the course of about 30 minutes, about 1 hour, about 90 minutes, orabout 2 hours. Prior to the addition of the glycidyl ester, TMAEE isheated to a temperature in the range of about 50° C. to about 250° C.While this reaction is exothermic, the initial temperature can bemaintained substantially constant during the addition of the glycidylester. In further aspect of the present invention, TMAEE is heated toand controlled at a temperature in the range of about 80° C. to about150° C. during the addition of the glycidyl ester.

Once the addition of the glycidyl ester is complete, the reactionmixture can controlled at a temperature in the range of about 50° C. toabout 250° C. In yet another aspect, the reaction mixture can becontrolled at a temperature in the range of about 80° C. to about 150°C. The time that it takes for this reaction to reach completion isdependent upon the reaction temperature. The reaction mixture can betested by gas chromatography (GC), or other analytical methods, todetermine when the ether compound having the formula (V)—in this case,TMAEE—has been completely consumed. It is within the scope of thepresent invention to use an excess of TMAEE reactant, or an excess ofthe glycidyl ester reactant. However, molar ratios that varysignificantly from a molar ratio of about 1:1 can lead to excess unusedreactants and potentially unwanted side reactions. A constructiveexample of the synthesis of a new compound having the formula (III) inaccordance with the present invention is illustrated in ConstructiveExample 7 that follows.

Compositions

In yet another aspect of the present invention, compositions areprovided that comprise at least one compound having the formula (IV):

wherein:

n in each occurrence is selected independently from 1, 2, or 3; and

R^(b) is:

or

-   -   c) a hydrogen atom;

R¹ is selected independently from a hydrogen atom or a substituted orunsubstituted C₁-C₅ alkyl or alkenyl group; and

R² and R³ are selected independently from a substituted or unsubstitutedC₁-C₂₄ alkyl, alkenyl, aryl, or aralkyl group.

When R^(b) is the ether moiety, the compounds have the formula (II):

wherein R¹, R², and n are as defined immediately above.

When R^(b) is the ester moiety, the compounds have the formula (III):

wherein R¹, R³, and n are as defined immediately above.

When R^(b) is a hydrogen atom, the compounds have the formula (V):

wherein n in each occurrence is selected independently from 1, 2, or 3.In one aspect, when n is 2 in each occurrence, the ether compound offormula (V) is N,N,N′-trimethyl-bis-(aminoethyl) ether (TMAEE). Inanother aspect, the ether compound of formula (V) isN,N-dimethylaminopropyl-N′-methylaminoethyl ether.

In a further aspect, the compositions comprising at least one compoundhaving the formula (IV) are catalyst compositions, with the proviso thatwhen n in each occurrence is 2, R^(b) is not a hydrogen atom. Thesecatalyst compositions can be employed to produce polyurethane gelsand/or foams. Also within the scope of the present invention arecompositions that comprise the contact product of at least one activehydrogen-containing compound and at least one compound having theformula (IV), with the proviso that when n in each occurrence is 2,R^(b) is not a hydrogen atom. In another aspect of the presentinvention, a composition is provided that comprises the contact productof at least one active hydrogen-containing compound and at least onecompound having the formula (IV), wherein when n in each occurrence isselected independently from 1, 2, or 3, R^(b) can be a hydrogen atom, anether group, or an ester group, as indicated above. In yet anotheraspect, a composition is provided that comprises the contact product ofat least one additive and at least one compound having the formula (IV),with the proviso that when n in each occurrence is 2, R^(b) is not ahydrogen atom. The at least one additive can be selected from at leastone crosslinker, at least one cell stabilizer, at least one flameretardant, at least one chain extender, at least one epoxy resin, atleast one acrylic resin, at least one filler, at least one pigment, orany combination thereof. In still another aspect of the presentinvention, a composition is provided that comprises the contact productof the at least one additive and at least one compound having theformula (IV), wherein when n in each occurrence is selectedindependently from 1, 2, or 3, R^(b) can be a hydrogen atom, an ethergroup, or an ester group, as indicated above.

Generally, polyurethane foam catalyst compositions can comprisecompounds which accelerate both the blowing (water-isocyanate) andgelling (polyol-isocyanate) reactions. It is beneficial to balance thesereactions in order to produce quality foams with acceptable properties.Compositions of the present invention can comprise a single compoundwhich accelerates, but keeps in balance, both the blowing and gellingreactions. Alternatively, the composition can further comprise at leastone catalyst that predominantly accelerates the blowing reaction (ablowing catalyst), at least one other catalyst that predominantlyaccelerates the gelling reaction (a gelling catalyst), or a combinationthereof. As described herein, a blowing catalyst is a catalyst thatpredominantly accelerates the blowing reaction, but can also, in certaincircumstances, accelerate the gelling reaction, albeit to a lesserdegree. Similarly, a gelling catalyst is a catalyst that predominantlyaccelerates the gelling reaction, but can also, in certaincircumstances, accelerate the blowing reaction, albeit to a lesserdegree.

Optional urethane catalysts that are suitable for use in thecompositions described herein include, but are not limited to, metalsalt catalysts, organometallic compounds, compounds with aminefunctionality, or combination thereof. Non-limiting metal salt catalystsand organometallic compounds include organotins, organobismuths, tinsalts, bismuth salts, and the like, or any combination thereof. Optionalamine compounds can include, for example, gelling catalysts such astriethylenediamine (TEDA), N-methylimidazole, 1,2-dimethylimidazole,N-methylmorpholine (commercially available as the DABCO® NMM catalyst),N-ethylmorpholine (commercially available as the DABCO® NEM catalyst),triethylamine (commercially available as the DABCO® TETN catalyst),N,N′-dimethylpiperazine,1,3,5-tris(dimethylaminopropyl)hexahydrotriazine (commercially availableas the Polycat® 41 catalyst), 2,4,6-tris(dimethylaminomethyl)phenol(commercially available as the DABCO TMR® 30 catalyst),N-methyldicyclohexylamine (commercially available as the Polycat® 12catalyst), pentamethyldipropylene triamine (commercially available asthe Polycat® 77 catalyst),N-methyl-N′-(2-dimethylamino)-ethyl-piperazine, tributylamine,dimethylaminocyclohexylamine (commercially available as the Polycat® 8catalyst), pentamethyldipropylene-triamine, triethanolamine,dimethylethanolamine, tris(3-dimethylamino)propylamine (commerciallyavailable as the Polycat® 9 catalyst), 1,8-diazabicyclo[5.4.0] undecene(commercially available as the DABCO® DBU catalyst or its acid blockedderivatives, and the like, as well as any combination thereof. Further,such optional urethane catalysts can include, for example, blowingcatalysts. Blowing catalysts include, but are not limited to,pentamethyldiethylenetriamine (commercially available as the Polycat® 5catalyst), hexamethyltriethylenetetramine,heptamethyltetraethylenepentamine, bis(dimethylaminoethyl)ether(commercially available as the DABCO® BL19 catalyst, and the like, aswell as any combination thereof. As noted earlier, some of theseoptional catalysts can accelerate both the gelling and blowingreactions. Additionally, some of these optional catalysts also canaccelerate the trimerization reaction, i.e., the reaction ofpolyisocyanates to form polyisocyanurates. Although not a requirement,compositions comprising compounds having the formula (IV) can furthercomprise other catalytic materials, such as carboxylate salts, which canaccelerate the trimerization reaction.

With respect to the present invention, when a quantity by weight of acatalyst composition is discussed, the quantity will include the totalamount of all catalysts, unless stated otherwise. As an example, if 0.8pphp of a gelling catalyst and 0.7 pphp of a blowing catalyst are usedin a given catalyst composition, the amount of the total polyurethanefoam catalyst is 1.5 pphp.

Polyisocyanates

Polyisocyanates that are useful in the polyurethane gel or foamformation process include, but are not limited to, hexamethylenediisocyanate, isophorone diisocyanate, phenylene diisocyante, toluenediisocyanate (TDI), diphenyl methane diisocyanate isomers (MDI),hydrated MDI and 1,5-naphthalene diisocyanate. For example, 2,4-TDI,2,6-TDI, and mixtures thereof, can be readily employed in the presentinvention. Other suitable mixtures of diisocyanates include, but are notlimited to, those known in the art as crude MDI, or PAPI, which contain4,4′-diphenylmethane diisocyanate along with other isomeric andanalogous higher polyisocyanates. In another aspect of this invention,prepolymers of polyisocyanates comprising a partially pre-reactedmixture of polyisocyanates and polyether or polyester polyol aresuitable. In still another aspect, the polyisocyanate comprises MDI, orconsists essentially of MDI or mixtures of MDI's. In yet another aspect,the polyisocyanate is MDI, TDI, or a combination thereof.

The compositions and the methods of making PUR foam of the presentinvention can be used to produce many types of foam. The compositionsare useful, for example, in the formation of foam products for rigid,semi-rigid, and flexible applications, each of which can require adifferent Isocyanate Index. As defined previously, Isocyanate Index isthe actual amount of polyisocyanate used divided by the theoreticallyrequired stoichiometric amount of polyisocyanate required to react withall the active hydrogen in the reaction mixture, multiplied by 100. Forpurposes of the present invention, Isocyanate Index is represented bythe equation: Isocyanate Index=(Eq NCO/Eq of active hydrogen)×100,wherein Eq NCO is the number of NCO functional groups in thepolyisocyanate, and Eq of active hydrogen is the number of equivalentactive hydrogen atoms.

Foam products which are produced with an Isocyanate Index from about 40to about 500 are within the scope of this invention. In accordance withother aspects of the present invention, the Isocyanate Index is fromabout 50 to about 300, from about 60 to about 200, or from about 70 toabout 115.

Polyols

Active hydrogen-containing compounds for use with the foregoingpolyisocyanates in forming the polyurethane foams of this invention canbe any of those organic compounds having at least two hydroxyl groupssuch as, for example, polyols. Polyols that are typically used in PURfoam formation processes include polyalkylene ether and polyesterpolyols. The polyalkylene ether polyol includes the poly(alkyleneoxide)polymers such as poly(ethyleneoxide) and poly(propyleneoxide) polymersand copolymers with terminal hydroxyl groups derived from polyhydriccompounds, including diols and triols, Polyols include, but are notlimited to, ethylene glycol, propylene glycol, 1,3-butane diol,1,4-butane diol, 1,6-hexane diol, neopentyl glycol, diethylene glycol,dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylolpropane, cyclohexane diol, sugars such as sucrose and like low molecularweight polyols, or a combination thereof.

Amine polyether polyols can be used in the present invention. These canbe prepared when an amine such as, for example, ethylenediamine,diethylenetriamine, tolylenediamine, diphenylmethanediamine, ortriethanolamine is reacted with ethylene oxide or propylene oxide.

In another aspect of the present invention, a single high molecularweight polyether polyol, or a mixture of high molecular weight polyetherpolyols, such as mixtures of di- and tri-functional materials and/ordifferent molecular weight or different chemical composition materialscan be used. In yet another aspect of the present invention, polyesterpolyols can be used, including those produced when a dicarboxylic acidis reacted with an excess of a diol. Non-limiting examples includeadipic acid or phathalic acid or phthalic anhydride reacting withethylene glycol or butanediol. Polyols useful in the present inventioncan be produced by reacting a lactone with an excess of a diol, forexample, caprolactone reacted with propylene glycol. In a furtheraspect, active hydrogen-containing compounds such as polyester polyolsand polyether polyols, and combinations thereof, are useful in thepresent invention.

In addition to polyester and polyether polyols, the masterbatches, orpremix compositions, frequently contain a polymer polyol. Polymerpolyols can be used, for example, in polyurethane foams to increase thefoam's resistance to deformation, i.e., to increase the load-bearingproperties of the foam. Suitable polymer polyols include, but are notlimited to, graft polyols, polyurea modified polyols, and the like, ormixtures thereof. A graft polyol can be a triol in which vinyl monomers,such as styrene and acrylonitrile, are graft copolymerized. A polyureamodified polyol can be a polyol containing a polyurea dispersion formedby the reaction of a diamine with TDI. TDI is used often in excess, sosome of the TDI may react with both the polyol and polyurea. A variationof the polyurea modified polyol is abbreviated PIPA polyol, and isformed by the in-situ polymerization of TDI and alkanolamine in thepolyol.

In another aspect, the at least one active hydrogen-containing compoundthat is useful in the compositions or formulations of the presentinvention is an at least one polyether polyol, at least one polyesterpolyol, at least one polymer polyol, or any combination thereof.Depending on the load-bearing requirements and the particular end-useapplication of the foam, polymer polyols can be absent from the premixor foam formulation, or can comprise up to about 100 percent of thepolyol portion of the premix or foam formulation. In another aspect,polymer polyols can comprise from about 10 percent to about 80 percent,or from about 25 percent to about 65 percent, of the polyol portion ofthe premix composition or foam formulation.

Blowing Agents

Blowing agents that can be used alone or in combination in the PUR foamformation process include, but are not limited to, water, methylenechloride, acetone, chlorofluorocarbons (CFCs), hydrofluorocarbons(HFCs), hydrochlorofluorocarbons (HCFCs), and hydrocarbons. Non-limitingexamples of HFCs include HFC-245fa, HFC-134a, and HFC-365. Illustrativeexamples of HCFCs include HCFC-141b, HCFC-22, and HCFC-123. Exemplaryhydrocarbons include n-pentane, iso-pentane, cyclopentane, and the like,or any combination thereof.

The amount of blowing agent used can vary based on, for example, theintended use and application of the foam product and the desired foamstiffness and density. In the foam formulations and methods forpreparing polyurethane foams of the present invention, the blowing agentis present in amounts from about 0.5 to about 20 parts by weight perhundred weight parts polyol (pphp), from about 1 to about 15 pphp, fromabout 1.5 to about 10 pphp, or from about 2 to about 5 pphp. If water ispresent in the formulation, for use as a blowing agent or otherwise,water is present in amounts up to about 20 pphp. In other words, watercan range from 0 to about 20 pphp. In another aspect, water can rangefrom 0 to about 15 pphp, from 0 to about 12 pphp, from 0 to about 8pphp, or from 0 to about 4 pphp.

Miscellaneous Additives

Depending upon on the requirements during foam manufacturing or for theend-use application of the foam product, various additives can beemployed in the compositions and PUR foam formulations to tailorspecific properties. These include, but are not limited to,crosslinkers, cell stabilizers, flame retardants, chain extenders, epoxyresins, acrylic resins, fillers, pigments, or any combination thereof.It is understood that other mixtures or materials that are known in theart can be included in the compositions and foam formulations and arewithin the scope of the present invention.

Suitable crosslinkers include, but are not limited to, diethanolamine,diisopropanolamine, triethanolamine, tripropanolamine, and the like, orany combination thereof. Crosslinkers also can function as urethanecatalysts due to the presence of an amine group in their chemicalstructure. Crosslinkers can be present in the foam formulation inamounts from about 0.05 to about 10 pphp, about 0.1 to about 8 pphp,about 0.2 to about 6 pphp, about 0.3 to about 4 pphp, about 0.4 to about3 pphp, or about 0.5 to about 2 pphp. Cell stabilizers includesurfactants such as organopolysiloxanes. Silicon surfactants can bepresent in the foam formulation in amounts from about 0.5 to about 10pphp, about 0.6 to about 9 pphp, about 0.7 to about 8 pphp, about 0.8 toabout 7 pphp, about 0.9 to about 6 pphp, about 1 to about 5 pphp, orabout 1.1 to about 4 pphp. Useful flame retardants include halogenatedorganophosphorous compounds and non-halogenated compounds. Anon-limiting example of a halogenated flame retardant istrichloropropylphosphate (TCPP). For example, triethylphosphate ester(TEP) and DMMP are non-halogenated flame retardants. Depending on theend-use foam application, flame retardants can be present in the foamformulation in amounts from 0 to about 50 pphp, from 0 to about 40 pphp,from 0 to about 30 pphp, or from 0 to about 20 pphp. In another aspect,the flame retardant is present from 0 to about 15 pphp, 0 to about 10pphp, 0 to about 7 pphp, or 0 to about 5 pphp. Chain extenders such asethylene glycol and butane diol can also be employed in the presentinvention.

Polyurethane and Polyurethane Foam Formulation and Process

The catalyst compositions according to the present invention cancatalyze the reaction between an isocyanate functionality and an activehydrogen-containing compound (e.g., an alcohol, a polyol, an amine,water) and especially the urethane (gelling) reaction of polyol hydroxylgroups with isocyanate to make polyurethanes and the blowing reaction ofwater with isocyanate to release carbon dioxide for making polyurethanefoam.

Catalyst compositions comprising at least one compound having theformula (IV) are present in the PUR gel or foam formulation in acatalytically effective amount. In the PUR formulations of the presentinvention, the catalyst composition is present in amounts from about0.01 to about 20 parts by weight per hundred weight parts of the atleast one active hydrogen-containing compound. In another aspect, thecatalyst composition is present in amounts from about 0.05 to about 15parts, from about 0.1 to about 10 parts, from about 0.15 to about 5parts, or from about 0.25 to about 2 parts, by weight per hundred weightparts of the at least one active hydrogen-containing compound. If the atleast one active hydrogen-containing compound is an at least one polyol,the catalyst composition is present in amounts from about 0.01 to about20 parts by weight per hundred weight parts polyol (pphp). In anotheraspect, the catalyst composition is present in amounts from about 0.05to about 15 pphp, about 0.1 to about 10 pphp, about 0.15 to about 5pphp, about 0.2 to about 4 pphp, or about 0.25 to about 2 pphp. Thecatalyst composition can further comprise additional urethane catalysts,such as gelling catalysts, blowing catalysts, or a combination thereof.

In accordance with the present invention, a method of making apolyurethane is provided that comprises contacting at least onepolyisocyanate with at least one active hydrogen-containing compound inthe presence of a catalytically effective amount of a catalystcomposition under conditions sufficient to produce the polyurethane. Theconditions sufficient to produce the polyurethane would be readily knownto one of ordinary skill in the art. In one aspect, the catalystcomposition comprises at least one compound having the formula (IV),with the proviso that when n in each occurrence is 2, R^(b) is not ahydrogen atom. In another aspect, the catalyst composition comprises atleast one compound having the formula (IV), wherein when n in eachoccurrence is selected independently from 1, 2, or 3, R^(b) can be ahydrogen atom, an ether group, or an ester group, as indicatedpreviously.

In a further aspect, a polyurethane foam can be produced by contactingat least one polyisocyanate and at least one active hydrogen-containingcompound in the presence of at least one blowing agent and acatalytically effective amount of a catalyst composition of the presentinvention under conditions sufficient to produce the polyurethane foam.The conditions sufficient to produce the polyurethane foam would bereadily known to one of ordinary skill in the art. For instance,activation of the blowing agent can occur at a specific reactiontemperature, or the blowing agent can react with isocyanate, forexample, if the blowing agent comprises water.

Additionally, the contacting of the at least one polyisocyanate and theat least one active hydrogen-containing compound in the presence of atleast one blowing agent and a catalytically effective amount of acatalyst composition in accordance with the present invention can occurin the presence of at least one additive selected from at least onecrosslinker, at least one cell stabilizer, at least one flame retardant,at least one chain extender, at least one epoxy resin, at least oneacrylic resin, at least one filler, at least one pigment, or anycombination thereof.

In accordance with the method of making polyurethane foam of the presentinvention, PUR foams can be produced having a tailored density. Foreexample, PUR foams can be produced having from about 20 Kg/m³ to about250 Kg/m³, from about 24 Kg/m³ to about 60 Kg/m³, or from about 35 Kg/m³to about 50 Kg/m³.

Optionally, in yet another aspect, the method of the present inventioncan produce PUR foams with no or substantially no undesirable amineodor. In this aspect, the method for preparing PUR foam has thermallystability up to about 80° C., about 100° C., about 120° C., or about150° C. In a still further aspect, the method of the present inventionproduces PUR foam that is substantially free of volatile amines and/oramine odors.

In accordance with one aspect of the method of the present invention,the components of the PUR foam formulation are contacted substantiallycontemporaneously. For example, at least one polyisocyanate, at leastone active hydrogen-containing compound, at least one blowing agent anda catalytically effective amount of a catalyst composition comprising atleast one compound having the formula (IV) are contacted together. Giventhe number of components involved in polyurethane formulations, thereare many different orders of combining the components, and one of skillin the art would realize that varying the order of addition of thecomponents falls within the scope of the present invention. As well, foreach of the different orders of combining the aforementioned componentsof the foam formulation, the foam formulation of the present inventioncan further comprise additional urethane catalysts. In addition, themethod of producing PUR foams can further comprise the presence of atleast one additive selected from at least one crosslinker, at least onecell stabilizer, at least one flame retardant, at least one chainextender, at least one epoxy resin, at least one acrylic resin, at leastone filler, at least one pigment, or any combination thereof. In oneaspect of the present invention, all of the components, includingoptional components, are contacted substantially contemporaneously.

In another aspect of the present invention, a premix of ingredientsother than the at least one polyisocyanate are contacted first, followedby the addition of the at least one polyisocyanate. For example, the atleast one active hydrogen-containing compound, the at least one blowingagent, and a catalyst composition comprising at least one compoundhaving the formula (IV) are contacted initially to form a premix. Thepremix is then contacted with the at least one polyisocyanate to producePUR foams in accordance with the method of the present invention. In afurther aspect of the present invention, the same method can beemployed, wherein the premix further comprises additional urethanecatalysts. Likewise, the premix can further comprise at least oneadditive selected from at least one crosslinker, at least one cellstabilizer, at least one flame retardant, at least one chain extender,at least one epoxy resin, at least one acrylic resin, at least onefiller, at least one pigment, or any combination thereof.

Yet another aspect of the present invention provides a method forpreparing a polyurethane foam comprising (a) forming a premixcomprising:

-   -   i) at least one polyol;    -   ii) zero to about 80 percent polymer polyol based on the at        least one polyol;    -   iii) about 0.5 to about 20 parts by weight per hundred weight        parts of the polyol (pphp) blowing agent;    -   iv) zero to about 20 pphp water;    -   v) about 0.05 to about 10 pphp crosslinker;    -   vi) about 0.5 to about 10 pphp silicon surfactant;    -   vii) zero to about 50 pphp flame retardant;    -   viii) about 0.01 to about 20 pphp of a catalyst composition        comprising at least one compound having the formula (IV); and        (b) contacting the premix with at least one polyisocyanate at an        Isocyanate Index from about 40 to about 500.

EXAMPLES

An exemplary polyurethane flexible foam formulation containing a gellingand a blowing catalyst such as the catalyst compositions according tothe present invention can comprise the components in parts by weight(pbw) shown in Table III. The general formulation in Table III wouldenable one of skill in the art to produce the polyurethane foamsillustrated in the examples with densities in the range of about 35Kg/m³ to about 50 Kg/m³. The catalyst quantity listed is the totalcatalyst amount, including both gelling and blowing catalysts, ifapplicable.

TABLE III Formulations of Foams in Examples 1-6 (catalyst varied).COMPONENT pbw Polyol  20-100 Polymer Polyol  0-80 Silicone Surfactant  1-2.5 Blowing Agent   2-4.5 Crosslinker 0.5-2   Catalyst 0.25-2  Isocyanate Index  70-115

The foams of the following examples were produced in a 32-oz (951 ml)paper cup by adding the catalyst (or catalysts) into approximately 192grams of the premix formulation in Table III: polyol or polyols,surfactant, blowing agent, and crosslinker. This composition was mixedfor about 10 seconds (s) at about 6,000 RPM using an overhead stirrerfitted with a 2-inch (5.1 cm) diameter stirring paddle. Sufficientisocyanate (either MDI or TDI) was then added to achieve the desiredIsocyanate Index of about 100, and the formulation was mixed well forabout 6 seconds (s) at about 6,000 RPM using the same stirrer. The 32-ozcup was dropped through a hole in the bottom of a 128-oz (3804 ml) papercup on a stand. The hole was sized appropriately to catch the lip of the32-oz cup. The total volume of the foam container was about 160 oz (4755ml). Foams approximated this volume at the end of the PUR foam formingreaction.

In the following examples, various types and quantities of catalystswere used to produce PUR foams of the present invention. Although theamounts of each catalyst were not the same for each example, therespective catalyst quantities were chosen to provide similarproperties. Specifically, In Examples 1 and 2, the catalyst quantitieswere chosen to provide similar foam start time, rise time, and free risedensity. In Example 3, the catalyst quantities were chosen to matchphysical properties of the foams. In Examples 4-6, the catalystquantities were chosen to provide similar foaming performance, or asimilar foam height versus time profile, as measured by automated rateof rise equipment.

Example 1 Comparison of N,N,N′-trimethyl-bis-(aminoethyl) ether Catalystwith a Standard Catalyst in MDI Foams

Gelling catalyst standard 1 was a mixture of mono andbis-dimethylaminopropyl urea, commercially available as the DABCO®NE1070 catalyst from Air Products and Chemicals, Inc. (APCI). Blowingcatalyst standard 2 was N,N,N′-trimethyl-N′-hydroxyethyl-bis-aminoethylether. Inventive catalyst 3 was N,N,N′-trimethyl-bis-(aminoethyl) ether(TMAEE).

Table IV summarizes the MDI foaming results at an Isocyanate Index ofabout 100 using catalyst 3. Both gelling and blowing catalyst quantitiesare listed in pphp. Foams A and B were produced using a mixture of theblowing catalyst standard 2 and a gelling catalyst. Foam A used thegelling catalyst standard 1 at about 1.2 pphp, and Foam B used inventivecatalyst 3, TMAEE, at about 1.0 pphp. Foam B had similar foamingproperties to Foam A, as illustrated by the similar start time, risetime, and free rise density. Thus, catalyst 3 gave similar foamingperformance to the commercial catalyst, gelling catalyst standard 1.However, the data also indicates that catalyst 3, TMAEE, is more activethan the standard catalyst, since it provided similar foaming results ata lower addition level (about 1.0 pphp versus about 1.2 pphp).

This is further illustrated when comparing Foams C and D, which did notuse blowing catalyst standard 2. Foams C and D had similar start times,rise times, and free rise densities. However, catalyst 3 was used atabout 1.6 pphp, while gelling catalyst standard 1 was present at about2.1 pphp. This confirms the higher activity of inventive catalyst 3,TMAEE, as compared to a commercial standard gelling catalyst.

TABLE IV Comparison of catalyst 3 with a standard catalyst in MDI foamsCatalyst Foam A Foam B Foam C Foam D Gelling Catalyst 1.2 — 2.1 —Standard 1 (pphp) Blowing Catalyst 0.2 0.2 — — Standard 2 (pphp)Catalyst 3 (pphp) — 1.0 — 1.6 ^(a)Start Time (s) 11 13 14 13 ^(b)RiseTime (s) 60 61 60 60 ^(c)Free Rise Density 46 44 43 39 (Kg/m³) Notes:^(a)Start time is the time in seconds that it takes the foam formulationto increase its volume by 15%. ^(b)Rise time is the time in seconds thatit takes the foam to reach 98% of the final foam height. ^(c)Free risedensity, in units of Kg/m³, is the density of the foam calculated bymeasuring the total weight of the foam and dividing the weight by thefoam volume under free rise conditions.

Example 2 Comparison of N,N,N′-trimethyl-bis-(aminoethyl) ether Catalystwith a Standard Catalyst in TDI Foams

Gelling catalyst standard 1 and blowing catalyst standard 2 were thesame catalysts as described in Example 1. Similarly, inventive catalyst3 was N,N,N′-trimethyl-bis-(aminoethyl) ether (TMAEE).

Table V summarizes the TDI foam results at an Isocyanate Index of about100 using catalyst 3. Both gelling and blowing catalyst quantities arelisted in pphp. Foams E and F were produced using a mixture of theblowing catalyst standard 2 and a gelling catalyst. Foam E used thegelling catalyst standard 1 at about 0.7 pphp, and Foam F used inventivecatalyst 3, TMAEE, at about 0.5 pphp. Foam F had similar foamingproperties to Foam E, as illustrated by the similar start time, risetime, and free rise density. Thus, catalyst 3 gave similar foamingperformance to the commercial catalyst, gelling catalyst standard 1.However, the data also indicates that catalyst 3, TMAEE, is more activethan the standard catalyst, since it provided similar foaming results ata lower addition level (about 0.5 pphp versus about 0.7 pphp).

This is further illustrated when comparing Foams G and H, which did notuse blowing catalyst standard 2. Foams G and H had similar start times,rise times, and free rise densities. However, catalyst 3 was used atabout 1.0 pphp, while gelling catalyst standard 1 was present at about1.3 pphp. This confirms the higher activity of inventive catalyst 3,TMAEE, as compared to a commercial standard gelling catalyst.

TABLE V Comparison of catalyst 3 with a standard catalyst in TDI foamsCatalyst Foam E Foam F Foam G Foam H Gelling Catalyst 0.7 — 1.3 —Standard 1 (pphp) Blowing Catalyst 0.2 0.2 — — Standard 2 (pphp)Catalyst 3 (pphp) — 0.5 — 1.0 ^(a)Start Time (s) 11 12 11 11 ^(b)RiseTime (s) 81 78 85 78 ^(c)Free Rise Density 37 36 43 36 (Kg/m³) Notes:^(a)Start time is the time in seconds that it takes the foam formulationto increase its volume by 15%. ^(b)Rise time is the time in seconds thatit takes the foam to reach 98% of the final foam height. ^(c)Free risedensity, in units of Kg/m³, is the density of the foam calculated bymeasuring the total weight of the foam and dividing the weight by thefoam volume under free rise conditions.

Example 3 Physical Property Comparison of Foams Produced UsingN,N,N′-trimethyl-bis-(aminoethyl) ether Catalyst with Foams ProducedUsing a Standard Catalyst

Gelling catalyst standard 1 and blowing catalyst standard 2 were thesame catalysts as described in Example 1. Similarly, inventive catalyst3 was N,N,N′-trimethyl-bis-(aminoethyl) ether (TMAEE).

Table VI summarizes the physical properties of PUR foams made withinventive catalyst 3, and either MDI and TDI, and compared with currentindustry standards. As shown in Table VI and discussed above, catalyst 3is more active than the industry standard. Table VI also illustratesthat physical properties of the foam measured under humid agedconditions (e.g., HALL, HACS, etc.) produced with catalyst 3 arecomparable to those obtained with industry standard catalyst systems.

TABLE VI Physical property comparison of foams using catalyst 3 withfoams using a standard catalyst. ^(e)Molded ^(f)Blowing ^(g)Gelling^(i)40% CLD ^(l)HA ^(m)HA Density Cat. 2 Cat. 1 ^(h)Cat. 3 Ambient^(j)HALL ^(k)HACS Tensile Elongation ^(d)Iso Kg/m³ PPHP PPHP PPHP KPa %% KPa % MDI 50 0.2 1.2 12 −15 27 140 95 MDI 50 0.2 1.0 10 −12 24 135 97TDI 45 0.2 0.70 7.4 −6.5 12 42 33 TDI 45 0.2 0.50 7.2 −3.9 8 49 39Notes: ^(d)Iso is the polyisocyanate used in the foam formulation, MDIor TDI. ^(e)Molded density is the density of foam produced in a mold.^(f)Blowing Cat. 2 is the Blowing Catalyst Standard 2 of Examples 1 and2. ^(g)Gelling Cat. 1 is the Gelling Catalyst Standard 1 of Examples 1and 2. ^(h)Cat. 3 is the Inventive Catalyst 3 (TMAEE) of Examples 1 and2. ^(i)40% CLD Ambient is the compression load deflection when the foamis compressed to 40% of its initial volume. ^(j)HALL is Humid Aged LoadLoss, calculated according to the following equation:$\frac{{40\% \mspace{14mu} {Hardness}\mspace{14mu} ({final})} - {40\% \mspace{14mu} {Hardness}\mspace{14mu} ({initial})}}{40\% \mspace{14mu} {Hardness}\mspace{14mu} ({initial})}$^(k)HACS is Humid Aged Compression Set, calculated according to thefollowing equation: C_(t) = [(t_(o) − t_(f))/t_(o)] * 100, where C_(t)is equal to the compression set expressed as a percentage of theoriginal thickness, t_(o) is the original thickness of the test sample,and t_(f) is the final thickness of the test sample 30 minutes (+10, −0minutes) after removal from the test device. ^(l)HA Tensile is HumidAged Tensile Strength, the tensile strength measured after aging thesample for 200 hours at 90° C. and 100% relative humidity. ^(m)HAElongation is Humid Aged Elongation, the elongation measured after agingthe sample for 200 hours at 90° C. and 100% relative humidity.

Example 4 Synthesis ofN,N,N′-trimethyl-N′-(2-hydroxypropyl-butylether)-bis-(aminoethyl) ether,and Comparison of its Performance as a Catalyst with a Standard Catalystin TDI Foams

Approximately 25 g (about 0.17 mol) of N,N,N′-trimethyl-bis-(aminoethyl)ether (abbreviated TMAEE) was placed in a 250-ml temperature-controlledflask with a stir bar and a reflux condenser. TMAEE was heated to about80° C. and controlled at that target temperature. While stirring theflask contents constantly, about 26.6 g (about 0.2 mol) of n-butylglycidyl ether were added slowly from an addition funnel to the flaskover a time period of about 1 hour. The n-butyl glycidyl ether iscommercially available as EPODIL® 741 from Air Products and Chemicals,Inc. (APCI). A mild exotherm was noted during the addition of then-butyl glycidyl ether.

Once the addition of the n-butyl glycidyl ether was complete, thereaction mixture was heated to a temperature of about 120° C. The flaskcontents were continuously stirred at this temperature for about 2hours. Using a gas chromatograph (GC), it was confirmed that TMAEE hadbeen completely consumed or reacted. The resulting reaction product,N,N,N′-trimethyl-N′-(2-hydroxypropyl-butylether)-bis-(aminoethyl) ether,constituted inventive catalyst 4. This compound is reflected in Table Ias formula A-11. The general reaction scheme is illustrated below:

Table VII lists the catalyst levels used to produce Foam J and Foam K atan Isocyanate Index of about 100. Gelling catalyst standard 1 was thesame catalyst as described in Example 1. Blowing catalyst standard 7 wasa mixture of N,N,N′-trimethyl-N′-hydroxyethyl-bis-(aminoethyl) ether andmono and bis-dimethylaminopropyl ureas, commercially available as theDABCO® NE210 catalyst from Air Products and Chemicals, Inc. (APCI).Inventive catalyst 4 wasN,N,N′-trimethyl-N′-(2-hydroxypropyl-butylether)-bis-(aminoethyl) ether.

FIG. 1 compares the foam height versus time for the standard orcomparative Foam J with Foam K, which was produced using a catalystmixture comprising about 0.33 pphp inventive catalyst 4 and about 0.70pphp gelling catalyst standard 1. As illustrated in FIG. 1, Foam K had afoam height versus time (rate of rise) profile that was very similar tothat of the standard Foam J. Thus, inventive catalyst 4 can providesimilar foaming performance to commercially available polyurethanecatalysts.

Example 5 Synthesis ofN,N,N′-trimethyl-N′-(2-hydroxypropyl-2-ethylhexylether)-bis-(aminoethyl)ether, and Comparison of its Performance as a Catalyst with a StandardCatalyst in TDI Foams

Approximately 25 g (about 0.17 mol) of TMAEE was placed in a 250-mltemperature-controlled flask with a stir bar and a reflux condenser.TMAEE was heated to about 80° C. and controlled at that targettemperature. While stirring the flask contents constantly, about 35 g(about 0.19 mol) of 2-ethylhexyl glycidyl ether were added slowly froman addition funnel to the flask over a time period of about 1 hour. The2-ethylhexyl glycidyl ether is commercially available as EPODIL® 746from Air Products and Chemicals, Inc. (APCI). A mild exotherm was notedduring the addition of the 2-ethylhexyl glycidyl ether.

Once the addition of the 2-ethylhexyl glycidyl ether was complete, thereaction mixture was heated to a temperature of about 120° C. The flaskcontents were continuously stirred at this temperature for about 2hours. Using a gas chromatograph (GC), it was confirmed that TMAEE hadbeen completely consumed or reacted. The resulting reaction product,N,N,N′-trimethyl-N′-(2-hydroxypropyl-2-ethylhexylether)-bis-(aminoethyl)ether, constituted inventive catalyst 5. This compound is reflected inTable I as formula A-47. The general reaction scheme is illustratedbelow:

Table VII lists the catalyst levels used to produce Foam J and Foam L atan Isocyanate Index of about 100. Gelling catalyst standard 1 was thesame catalyst as described in Example 1. Blowing catalyst standard 7 wasthe same catalyst as described in Example 4. Inventive catalyst 5 wasN,N,N′-trimethyl-N′-(2-hydroxypropyl-2-ethylhexylether)-bis-(aminoethyl)ether.

FIG. 2 compares the foam height versus time for the standard orcomparative Foam J with Foam L, which was produced using a catalystmixture comprising about 0.43 pphp inventive catalyst 5 and about 0.70pphp gelling catalyst standard 1. As illustrated in FIG. 2, Foam L had afoam height versus time (rate of rise) profile that was almost identicalto that of the standard Foam J. Thus, inventive catalyst 5 can providesimilar foaming performance to commercially available polyurethanecatalysts.

Example 6 Synthesis ofN,N,N′-trimethyl-N′-(2-hydroxypropyl-dodecylether)-bis-(aminoethyl)ether andN,N,N′-trimethyl-N′-(2-hydroxypropyl-tetradecylether)-bis-(aminoethyl)ether, and Comparison of their Performance as a Mixed Catalyst with aStandard Catalyst in TDI Foams

Approximately 25 g (about 0.17 mol) of TMAEE was placed in a 250-mltemperature-controlled flask with a stir bar and a reflux condenser.TMAEE was heated to about 80° C. and controlled at that targettemperature. While stirring the flask contents constantly, about 50.8 gof a mixture of approximately 75% dodecyl glycidyl ether andapproximately 25% tetradecyl glycidyl ether (C₁₂ and C₁₄ glycidylethers) were added slowly from an addition funnel to the flask over atime period of about 1 hour. The approximate 75% C₁₂/25% C₁₄ glycidylether blend is commercially available as EPODIL® 748 from Air Productsand Chemicals, Inc. (APCI). A mild exotherm was noted during theaddition of the C₁₂/C₁₄ glycidyl ether blend.

Once the addition of the C₁₂/C₁₄ glycidyl ether blend was complete, thereaction mixture was heated to a temperature of about 120° C. The flaskcontents were continuously stirred at this temperature for about 2hours. Using a gas chromatograph (GC), it was confirmed that TMAEE hadbeen completely consumed or reacted. The resulting reaction productmixture,N,N,N′-trimethyl-N′-(2-hydroxypropyl-dodecylether)-bis-(aminoethyl)ether andN,N,N′-trimethyl-N′-(2-hydroxypropyl-tetradecylether)-bis-(aminoethyl)ether, constituted inventive catalyst 6. These compounds are reflectedin Table I as formulas A-65 and A-71. The general reaction scheme isillustrated below:

Table VII lists the catalyst levels used to produce Foam J and Foam M atan Isocyanate Index of about 100. Gelling catalyst standard 1 was thesame catalyst as described in Example 1. Blowing catalyst standard 7 wasthe same catalyst as described in Example 4. Inventive catalyst 6 was amixture ofN,N,N′-trimethyl-N′-(2-hydroxypropyl-dodecylether)-bis-(aminoethyl)ether andN,N,N′-trimethyl-N′-(2-hydroxypropyl-tetradecylether)-bis-(aminoethyl)ether.

FIG. 3 compares the foam height versus time for the standard orcomparative Foam J with Foam M, which was produced using a catalystmixture comprising about 0.65 pphp inventive catalyst 6 and about 0.70pphp gelling catalyst standard 1. As illustrated in FIG. 3, Foam M had afoam height versus time (rate of rise) profile that was very similar tothat of the standard Foam J. Thus, inventive catalyst 6 can providesimilar foaming performance to commercially available polyurethanecatalysts.

TABLE VII Catalysts used in the Foam Formulations of Examples 4-6Catalyst Foam J Foam K Foam L Foam M Gelling Catalyst 0.19 0.70 0.700.70 Standard 1 (pphp) Blowing Catalyst 0.68 — — — Standard 7 (pphp)Catalyst 4 (pphp) — 0.33 — — Catalyst 5 (pphp) — — 0.43 — Catalyst 6(pphp) — — — 0.65

Constructive Example 7 Constructive Synthesis ofN,N,N′-trimethyl-N′-(2-hydroxypropyl-butylester)-bis-(aminoethyl) ether,and Constructive Comparison of its Performance as a Catalyst with aStandard Catalyst in MDI or TDI Foams

First, place approximately 25 g (about 0.17 mol) of TMAEE in a 250-mltemperature-controlled flask with a stir bar and a reflux condenser.Heat TMAEE to about 80° C. and control at that target temperature. Whilestirring the flask contents constantly, add about 0.17 mol of n-butylglycidyl ester slowly from an addition funnel to the flask over a timeperiod of about 1 hour. The molar ratio of TMAEE to the glycidyl estershould be close to 1:1. A mild exotherm should be observed during theaddition of the n-butyl glycidyl ester.

Once the addition of the n-butyl glycidyl ester is complete, heat thereaction mixture to a temperature of about 120° C. Stir the flaskcontents substantially continuously at this temperature for about 2hours. A gas chromatograph (GC) can be employed to confirm that theTMAEE is completely consumed or reacted. The resulting reaction product,N,N,N′-trimethyl-N′-(2-hydroxypropyl-butylester)-bis-(aminoethyl) ether,will constitute inventive catalyst 7. This compound is reflected inTable II as formula B-05.

Foams can be produced at an Isocyanate Index of about 100 using catalystlevels similar to those illustrated in Table VII and using the foamformulation illustrated in Table III. Gelling catalyst standard 1 can bethe same catalyst as described in Example 1 and used at a level of about0.7 pphp. Blowing catalyst standard 7 can be the same catalyst asdescribed in Example 4. Inventive catalyst 7 will beN,N,N′-trimethyl-N′-(2-hydroxypropyl-butylester)-bis-(aminoethyl) etherand can be used a level of about 0.3 to about 0.5 pphp, chosen to matchthe foaming performance of the standard formulation (e.g., Foam J inTable VII). One or ordinary skill in the art would be able to producepolyurethane foams with densities in the range of about 35 Kg/m³ toabout 50 Kg/m³.

The foams can be produced in a 32-oz (951 ml) paper cup by adding thecatalyst (or catalysts) into approximately 192 grams of the premixformulation in Table III: polyol or polyols, surfactant, blowing agent,and crosslinker. This composition is then mixed for about 10 seconds (s)at about 6,000 RPM using an overhead stirrer fitted with a 2-inch (5.1cm) diameter stirring paddle. Sufficient isocyanate (either MDI or TDI)is added to achieve the desired Isocyanate Index of about 100, and theformulation is mixed well for about 6 seconds (s) at about 6,000 RPMusing the same stirrer. The 32-oz cup then is dropped through a hole inthe bottom of a 128-oz (3804 ml) paper cup on a stand. The hole shouldbe sized appropriately to catch the lip of the 32-oz cup. The totalvolume of the foam container is about 160 oz (4755 ml). Foams canapproximate this volume at the end of the PUR foam forming reaction.Foaming performance of inventive catalyst 7 can be evaluated bycomparing the foam height versus time profile versus that of standardFoam J, as is shown in FIGS. 1-3 pertaining to Examples 4-6. Foam heightprofiles can be measured by automated rate of rise equipment.

1-32. (canceled)
 33. A catalyst composition for use with reacting anisocyanate and at least one polyol to produce a polyurethane foamwherein the catalyst composition comprises at least one gelling catalystcomprising at least one compound having the formula:

wherein: n in each occurrence is selected independently from 1, 2, or 3;R^(b) is a hydrogen atom; and at least one blowing catalyst, wherein theblowing catalyst is N,N,N′-trimethyl-N′-hydroxyethyl-bis-aminoethylether.
 34. The catalyst composition of claim 33, further comprising atleast one additive selected from at least one cell stabilizer, at leastone flame retardant, at least one chain extender, at least one epoxyresin, at least one acrylic resin, at least one filler, at least onepigment, or any combination thereof.
 35. The catalyst composition ofclaim 33, wherein the at least one polyol comprises at least onepolyether polyol, at least one polyester polyol, at least one polymerpolyol, or any combination thereof.
 36. The catalyst composition ofclaim 33, further comprising at least one member selected from the groupconsisting of triethylenediamine, N-methylimidazole,1,2-dimethylimidazole, N-methylmorpholine, N-ethylmorpholine,trimethylamine N,N′dimethylpiperazine,1,3,5-tris(dimethylaminopropyl)hexahydrotriazine,2,4,6-tris(dimethylaminomethyl)phenol, N-methyldicyclohexylamine,pentamethyldipropylene triamine,N-methyl-N′-(2-dimethylamino)-ethyl-piperazine, tributylamine,dimethylaminocyclohexylamine, pentamethyldipropylene-triamine,triethanolamine, dimethylethanolamine, tris(3-dimethylamino)propylamine,and 1,8 diazabicyclo[5.4.0] undecene.
 37. The catalyst composition ofclaim 33, further comprising at least one additive selected from atleast one cell stabilizer, at least one flame retardant, at least oneepoxy resin, at least one acrylic resin, at least one filler, at leastone pigment, or any combination thereof.
 38. The catalyst composition ofclaim 33, wherein the catalyst composition further comprises at leastone member selected from the group consisting of metal salt catalysts,and organometallic compounds.
 39. The catalyst composition of claim 33,further comprising at least one member selected from the groupconsisting of diethanolamine, diisopropanolamine, triethanolamine, andtripropanolamine.
 40. The catalyst composition of claim 33, furthercomprising at least one silicon surfactant.
 41. The catalyst compositionof claim 37, wherein the at least one additive is a flame retardantselected from the group consisting of organophosphorous compounds andnon-halogenated compounds.
 42. The catalyst composition of claim 34,wherein the at least one additive is a chain extender selected from thegroup consisting of ethylene glycol and butane diol.
 43. The catalystcomposition of claim 33, wherein n=2.
 44. The catalyst composition ofclaim 33 wherein the catalyst composition has a thermal stability up toabout 150 degrees C.
 45. The catalyst composition of claim 33 whereinthe catalyst composition has a thermal stability up to about 120 degreesC.
 46. The catalyst composition of claim 33 wherein the catalystcomposition has a thermal stability up to about 100 degrees C.
 47. Acatalyst composition for use with reacting an isocyanate and at leastone polyol to produce a polyurethane foam wherein the catalystcomposition comprises at least one gelling catalyst comprising at leastone compound having the formula:

wherein: n in each occurrence is selected independently from 1, 2, or 3;R^(b) is a hydrogen atom; and at least one blowing catalyst, wherein theblowing catalyst is selected from the group consisting ofbis(dimethylaminoethyl)ether, pentamethyldiethylenetriamine,hexamethyltriethylenetetramine, and heptamethyltetraethylenepentamine.